Organic Letters,
Год журнала:
2022,
Номер
24(7), С. 1471 - 1475
Опубликована: Фев. 15, 2022
The
gem-difluoroalkene
moiety
is
an
ideal
carbonyl
bioisostere
in
medicinal
chemistry,
but
efficient
synthesis
of
β-gem-difluoroalkene
esters
remains
challenging
so
far.
Herein,
we
disclose
a
photoredox-catalyzed
allylic
defluorinative
alkoxycarbonylation
trifluoromethyl
alkenes
enabled
by
intermolecular
alkoxycarbonyl
radical
addition.
A
wide
variety
alcohol
oxalate
derivatives
were
amenable,
affording
various
with
excellent
functional
group
tolerance.
Notably,
the
potential
synthetic
value
this
method
highlighted
successful
late-stage
modification
for
bioactive
molecules.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(38)
Опубликована: Июль 21, 2022
Abstract
Highly
selective
and
direct
electroreductive
ring‐opening
carboxylation
of
epoxides
with
CO
2
in
an
undivided
cell
is
reported.
This
reaction
shows
broad
substrate
scopes
within
styrene
oxides
under
mild
conditions,
providing
practical
scalable
access
to
important
synthetic
intermediate
β
‐hydroxy
acids.
Mechanistic
studies
show
that
functions
not
only
as
a
carboxylative
reagent
this
but
also
promoter
enable
efficient
chemoselective
transformation
additive‐free
electrochemical
conditions.
Cathodically
generated
α
‐radical
‐carbanion
intermediates
lead
the
regioselective
formation
‐carboxylation
products.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(9), С. 2522 - 2528
Опубликована: Янв. 1, 2022
A
photocatalytic
protocol
for
the
synthesis
of
β-amino
acid
ester
and
ketone
derivatives
is
developed
using
simple
easy-to-synthesize
oxime
oxalate
phenylglyoxylate
as
difunctionalization
reagents.
Organic Letters,
Год журнала:
2022,
Номер
24(19), С. 3565 - 3569
Опубликована: Май 9, 2022
Direct
electrocarboxylation
of
various
N-acylimines
with
atmospheric
CO2
is
achieved
in
an
undivided
cell
under
mild
conditions,
affording
substituted
α-amino
acids
yields
62–95%.
This
reaction
conducted
high
efficiency
using
triethanolamine
as
external
reductant
nonsacrificial
anode
and
can
be
facilely
performed
on
gram
scale.
Preliminary
mechanistic
studies
including
cyclic
voltammetry
control
experiments
support
N-radical
carbanion
the
key
intermediate.
Organic Letters,
Год журнала:
2022,
Номер
24(7), С. 1471 - 1475
Опубликована: Фев. 15, 2022
The
gem-difluoroalkene
moiety
is
an
ideal
carbonyl
bioisostere
in
medicinal
chemistry,
but
efficient
synthesis
of
β-gem-difluoroalkene
esters
remains
challenging
so
far.
Herein,
we
disclose
a
photoredox-catalyzed
allylic
defluorinative
alkoxycarbonylation
trifluoromethyl
alkenes
enabled
by
intermolecular
alkoxycarbonyl
radical
addition.
A
wide
variety
alcohol
oxalate
derivatives
were
amenable,
affording
various
with
excellent
functional
group
tolerance.
Notably,
the
potential
synthetic
value
this
method
highlighted
successful
late-stage
modification
for
bioactive
molecules.
